Laws Of Thermodynamics

The first law of thermodynamics is a statement of the law of conservation of energy:

– Energy can be neither created nor destroyed. In other words, the energy of the
universe is constant.
Energy in Chemical Reactions

A+B C + D + Energy

• The potential energy is broken in chemical bonds in compounds A and B

• The potential energy is the chemical bonds of C and D is lower

The excess has been given off (energy) as thermal energy, or heat, which is kinetic
energy transferred to the surroundings
Spontaneity
 Spontaneous Processes
• Processes that occur without outside intervention
• Spontaneous processes may be fast or slow
– Many forms of combustion are fast
– Conversion of graphite to diamond is slow
– Kinetics is concerned with speed, thermodynamics with the initial and final state
 2nd Law of Thermodynamics
 2nd Law introduces entropy, S

Reversible Irreversible
 Some of the enthalpy in a system is not convertible into work (PdV work for
instance) because it is consumed by an increase in entropy
 Which could be restated that is requires some amount of work to increase entropy
 NEED FOR THE SECOND LAW
 The First Law of Thermodynamics tells us that during any process, energy must be
conserved.
 However, the First Law tells us nothing about in which direction a process will
proceed spontaneously.
 It would not contradict the First Law if a book suddenly jumped off the table and
maintained itself at some height above the table.
 It would not contradict the First Law if all the oxygen molecules in the air in this
room suddenly entered a gas cylinder and stayed there while the valve was open.
THE SECOND LAW IN WORDS
 experience tells us that certain processes only run spontaneously in one direction or the other.
 This allows us to deduce the Second Law.
 The Kelvin formulation - It is impossible to construct an engine that, working in cycles, shall
produce no effect other than the extraction of heat from a reservoir and the production of work.
 The Clausius formulation - It is impossible to construct an engine that, working in cycles, shall
produce no effect other than the transfer of heat from a colder to a hotter body.
MEANING OF ENTROPY AND THE SECOND LAW
 Entropy is a measure of the disorder (randomness) of a system. The higher the entropy of the
system, the more disordered it is.
 The second law states that the universe always becomes more disordered in any real process.
 The entropy (order) of a system can decrease, but in order for this to happen, the entropy
(disorder) of the surroundings must increase to a greater extent, so that the total entropy of the
universe always increases.
• Combining the 1st and 2nd Laws of
Thermodynamics:
dU = dqrev + dw = TdS – PdV
• If a process is at constant volume, V, and entropy, S
then, dU = 0, nothing happens, energy does not
change in the system
• This is EQUILIBRIUM:
– dU > 0 spontaneous reaction products to reactants
– dU < 0 spontaneous reaction reactants to products
Entropy (S)

• A measure of the randomness or disorder

• The driving force for a spontaneous process is an increase in the entropy of the
universe (one of the laws of thermodynamics!)

– The universe favors chaos!!

• Entropy is a thermodynamic function describing the number of arrangements that

are available to a system

• Nature proceeds towards the states that have the highest probabilities of existing
"In any spontaneous process there is always an increase in the entropy of the universe"
"The entropy of the universe is increasing"
For a given change to be spontaneous, Suniverse must be positive
Suniv = Ssys + Ssurr
 Entropy and Temperature

Suniv = Ssys + Ssurr

• Entropy changes in the surrounding are primarily determined by heat flow

• The magnitude of entropy is dependent on the temperature

• The lower the temperature, the higher the impact to the surroundings of the transfer
of energy
Entropy and Exothermic Processes
• Entropy and a process being exothermic are related, but a process doesn’t have to
be both
• Exothermic process
– Ssurr = positive, exothermic = more disorder in surroundings
• Endothermic process
– Ssurr = negative, endothermic = less disorder in surroundings
– Ssystem must increease to obey 2nd Law of Thermodynamics
More on Entropy

 Why is the sign different?

– The enthalpy (H) concerns the system
– Our entropy here concerns the surroundings
– As usual, temperatures must be in Kelvin

Example
First Reaction

H = -125 kJ, T = 25 oC + 273 = 298 K

Ssurr = -125 kJ/298 K = 419 J/K

Second Reaction
H = 778 kJ, T = 25 oC + 273 = 298 K
S = 778 kJ/298 K = -2.61 kJ/K
 Free Energy, G (G = H - TS)
• Typically defined as the energy available to perform work
• G determines whether a process is spontaneous or not. Takes into account
enthalpy, entropy, and temperature
Energy Diagrams

• Left – A spontaneous reaction

– The products have a lower free energy (G) than the reactants (DG < 0)
• Right – A nonspontaneous reaction
– The reactants have a higher free energy than the products (DG > 0)
What If?

• G < 0 The reaction is spontaneous.

• G > 0 The reaction is non-spontaneous.

• G = 0 The reaction mixture is at equilibrium.

It’s not moving forward or reverse overall – multiple processes, same speed
Dependence on Temperature
G = H - TS
• Notice there are two terms in the equation

– Spontaneity can change when the temperature changes.

– Temperature and spontaneity are not necessarily correlated.

• A reaction with a negative entropy (loss of randomness) would be LESS

spontaneous at higher temperatures – it doesn’t want to happen, but is
pushed by the extra heat.
Reaction Rates

• Free energy (G) values tell us if reactions will occur

• They do not tell us how fast reactions will occur.

• During a reaction

– Reactant particles must physically collide

– They must collide with enough energy to break the bonds in the reactant

• Some reactions require the addition of heat energy. This gives the
reactants the extra energy needed (more collisions, harder collisions) for
this process to occur.
H, S, G and Spontaneity
G = H - TS, H is enthalpy, T is Kelvin temperature

Value of Value of Value of Spontaneity

H T S G

Negative Positive Negative Spontaneous

Positive Negative Positive Nonspontaneous

Negative Negative ??? Spontaneous if the absolute
value of H is greater than
the absolute value of TS
(low temperature)
Positive Positive ??? Spontaneous if the absolute
value of TS is greater than
the absolute value of H
(high temperature)
 Example of Gibbs Energy

• For the reaction at 298 K, the values of H and S are 58.03 kJ and
176.6 J/K, respectively. What is the value of G at 298 K?
• G = H - TS
• G = 58.03 kJ – (298 K)(176.6 J/K)
• G = 5.40 kJ Not spontaneous at this temperature
Second Example
Calculate the standard free-energy change at 25 oC for the Haber synthesis of
ammonia using the given values for the standard enthalpy and standard entropy
changes: N2(g) + 3H2(g) 2NH3(g) Ho = 92.2 kJ
So = 198.7 J/K
G = H  TS
G = 92.2 kJ  (298 K)(-198.7 J/K)(1 kJ/1000 J)
= -33.0 kJ
Third Example
Iron metal can be produced by reducing iron(III) oxide with hydrogen:
Fe2O3(s) + 3 H2(g)  2 Fe(s) + 3 H2O(g) H = +98.8 kJ; S = +141.5 J/K
(a) Is this reaction spontaneous under standard-state conditions at 25 °C?
(b) At what temperature will the reaction become spontaneous?
• To determine whether the reaction is spontaneous at 25 °C, we need to
determine the sign of G = H  TS. At 25 C (298 K), G for the reaction is

G = H  TS = (98.8 kJ)  (298 K)(0.1415 kJ/K)

= (98.8 kJ)  (42.2 kJ)
= 56.6 k
Reaction is NOT spontaneous!
 At what temperature does this become spontaneous?

• At temperatures above 698 K, the TS term becomes larger than H, making the
Gibbs energy negative and the process spontaneous

 Why is this postive this time?

– Remember, here we’re dealing with the system, not the surroundings!
Entropy Changes in Chemical Reactions

 Constant Temperature and Pressure

– Reactions involving gaseous molecules

• The change in positional entropy is dominated by the relative numbers of

molecules of gaseous reactants and products

Typically, more moles of gas, more entropy

 Third Law of Thermodynamics
• "The entropy of a perfect crystal at O K is zero" (NO disorder,
since everything is in perfect position)

– No movement = 0 K

– No disorder = no entropy (S = 0)

• Standard State Conditions
• We’ve seen that quantities such as entropy (S), enthalpy (H), and free
energy (G) are dependent upon the conditions present
• Standard State
– One set of conditions at which quantities can be compared
• Pure solids/liquids/gases at 1 atm pressure
• Solutes at 1 M concentration
• Typically at 25 oC (298 K)
• Designated by o sign (similar to degree sign)
Calculating Entropy Change in a Reaction

Sreaction
0
  np Sproducts
0
  nr Sreactants
o

 Calculates standard entropy of a reaction, uses standard entropies of compounds

 Entropy is an extensive property (a function of the number of moles)
 Generally, the more complex the molecule, the higher the standard entropy value
 Calculating Standard Entropy - Example

S 0
reaction  n S0
p products   nr S
o
reactants
• 2 (28 J/Kmol) + 3 (189 J/Kmol) – 51 J/K mole – 3 (131
J/Kmol) = 179 J/K
• System gained entropy – water more complex than
hydrogen!
 Second Example
• Evaluate the entropy change for the reaction:
CO + 3 H2 -> CH4 + H2O
in which all reactants and products are gaseous.
So values: CO 198 J/Kmol
H2 131 J/Kmol
CH4 186 J/Kmol
H2O 189 J/Kmol

So reaction = [186 + 189] – [198 + 3(131)] = 216 J/Kmol

 Standard Free Energy Change
• G0 is the change in free energy that will occur
if the reactants in their standard states are
converted to the products in their standard
states
– G0 cannot be measured directly
– The more negative the value for G0, the farther to
the right the reaction will proceed in order to
achieve equilibrium
– Equilibrium is the lowest possible free energy
position for a reaction
Calculating Free Energy of Formation
Using standard free energy of formation (Gf0):

G   np G
0 0
f (products)   nr G 0
f (reactants)

Gf0 of an element in its standard state is zero!

 Calculating Free Energy of Formation - Example

G0   np G0f (products)   nr G0f (reactants)

• 2 (-394kJ/mol) + 4 (-229 kJ/mol) – 2 (-163

kJ/mol) – 3 (0) = - 1378 kJ
 Second Example
• Calculate the standard free energy for the
reaction below and determine whether it is
spontaneous at standard conditions.

Fe2O3(s) + 3 CO (g) 2 Fe (s) + 3 CO2(g)

Go (kJ/mol)= -742.2 -137.2 0 -394.4

Go = [0 + (3 x -394.4)] – [-742.2 + (3 x -137.2)] =

-29.4 kJ/mol
 The Dependence of Free Energy on Pressure

Enthalpy, H, is not pressure dependent

Entropy, S
 entropy depends on volume, so it also depends
on pressure
Slarge volume > Ssmall volume
Slow pressure > Shigh pressure
 Free Energy and Equilibrium
G = Go + RTln(Q)
Go = -RTln(K) at equilibrium
• R = Universal gas constant = 8.314 J/K mol
• T = Temperature in Kelvin
• K = Equilibrium constant = [Pproducts]/[Preactants]
• System is at equilbrium (no net movement)
when Go = 0 (K = 1)
• If the system is NOT at equilibrium, use Q
instead of K
 Example

• For the synthesis of ammonia where Go = -33.3 kJ/mole, determine

whether the reaction is spontaneous at 25 C with the following
pressures:
PN2 = 1.0 atm, PH2 = 3.0 atm, PNH3 = 0.020 atm

G = Go + RTln(Q)
G = -33.3 kJ/mole + (8.314 J/K mol)(298 K) ln([0.02 atm]2)
___________________

[1.0 atm][3.0 atm]3

G = -33.3 kJ/mole + (8.314 J/K mol)(298 K) ln(1.5 x 10-5)

G = -60.5 kJ/mol
 Example

• The synthesis of methanol from carbon dioxide and hydrogen has a Go = -
25.1 kJ/mol. What is the value of the equilibrium constant at 25 oC?

G = Go + RTln(K)
Go = - RTln(K)
-25.1 kJ/mol = -(8.314 J/molK)(298)lnK
Solve for ln K = 10.1, K = 2 x 104